Professional Documents
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in
Encyclopedia of Analytical Chemistry
R.A. Meyers (Ed.)
pp. 13644–13670
John Wiley & Sons Ltd, Chichester, 2000
ULTRAFAST LASER TECHNOLOGY AND SPECTROSCOPY 1
Ultrafast Laser Technology and transition states. Ultrafast lasers can also be used
to produce laser pulses with enormous peak powers and
and Spectroscopy power densities. This leads to applications such as laser
machining and ablation, generation of electromagnetic
radiation at unusual wavelengths (such as millimeter waves
Gavin D. Reid and X-rays), and multiphoton imaging. The difficulty
University of Leeds, Leeds, UK in applying femtosecond laser pulses is that the broad
Klaas Wynne frequency spectrum can lead to temporal broadening of
University of Strathclyde, Glasgow, UK the pulse on propagation through the experimental set-up.
In this article, we describe the generation and amplification
of femtosecond laser pulses and the various techniques that
have been developed to characterize and manipulate the
1 Introduction 1 pulses.
2 Ultrafast Lasers and Amplifiers 2
2.1 Oscillators 2
2.2 Dispersion and Pulse Broadening 3 1 INTRODUCTION
2.3 Chirped-pulse Amplification 6
2.4 Pulse Recompression 8
Ultrafast spectroscopy has become one of the most active
2.5 Saturation Effects 9
areas of physical chemistry. Rather than postulating
3 Wavelength Conversion 9 mechanisms for chemical and biological reactions, ultra-
3.1 White-light Generation and the short laser pulses can now be used to observe and even
Optical Kerr Effect 9 control the outcome of reactions in real time. Because
3.2 Generation of Ultraviolet and of our improved understanding of reaction pathways,
X-rays 10 the ‘‘arrows’’ describing purported electronic motion in
3.3 Optical Parametric Amplifier for mechanistic organic chemistry are no longer sufficient..1/
Infrared Generation 11 A state-of-the-art laser system can generate 1-J ca. 20-fs
3.4 Noncollinear Optical Parametric pulses and the peak fluence at the focus of these lasers can
Amplification 12 exceed 1020 W cm 2 . In contrast, the total solar flux at the
3.5 Terahertz-pulse Generation and Earth is only 1017 W. An exciting new era is beginning,
Detection 12 which will allow the possibility of using these intense
3.6 Femtosecond Electron Pulses 14 ultrashort laser pulses as sources of short X-ray and elec-
4 Time-resolved Experiments 14 tron pulses. These will reveal the positions of atoms as a
4.1 Auto- and Cross-correlation 14 function of time as reactants proceed to products through
4.2 Pump – Probe Techniques 17 the transition states. More routinely, femtosecond lasers
5 Applications 18 can be used to detect and monitor transient chemical
5.1 The Study of Fast Chemical species in solution or the gas phase, to image living cells
Reactions 18 with micrometer resolution, for laser ablation mass spec-
5.2 Imaging 20 trometry (MS) and micromachining applications, which
5.3 Structure Determination: Electron will all be of immediate interest to the analytical chemist.
Beams and X-rays 21 With the invention of flash photolysis in 1950,.2/ radical
intermediates were observed by light absorption (rather
Acknowledgments 22
than fluorescence) during the progress of a chemical
Abbreviations and Acronyms 22 reaction. When the pulsed laser followed, nanosecond
Related Articles 22 experiments derived from the flash-photolysis technique
References 23 were to reveal the chemistry of singlet states in solution.
However, it was not until the mode-locked ruby.3/ and
Nd : glass.4/ lasers were built in the mid-1960s that the
picosecond timescale became accessible and the field of
Ultrafast laser technology and spectroscopy involves the ‘‘picosecond phenomena’’ was born. When excited-state
use of femtosecond (10 15 s) laser and other (particle) processes were studied in the picosecond domain, such as
sources to study the properties of matter. The extremely energy redistribution in molecules and proteins, proton
short pulse duration allows one to create, detect and study and electron transfer reactions, photoisomerization and
very short-lived transient chemical reaction intermediates dissociation, and relaxation in semiconductors, many
measured rate constants were found to be instrument when many longitudinal modes are held in phase in a
limited. Nevertheless, important results such as the laser resonator. Various techniques have been employed,
observation of the ‘‘inverted region’’ in electron transfer usually grouped under the terms ‘‘active’’ or ‘‘passive’’
reactions.5 – 7/ and Kramers’ turnover in excited-state mode locking and descriptions of these can be found in
reactions in solution..8,9/ many standard texts.18,19/ and review articles..20/ Active
However, ultrafast spectroscopy was revolutionized in mode locking uses a modulator in the laser cavity whereas
the 1980s by the invention of the colliding-pulse mode- passive schemes use a saturable absorber, often a thin
locked (CPM) dye laser, which generated 100-fs pulses semiconductor film, to lock the relative phases. Modern
in its early form.10/ and 30-fs pulses as the technology solid-state mode-locked lasers use a different scheme
was perfected..11/ This ring laser, operating at about called self-mode-locking and titanium-doped sapphire
620 nm, coupled with improvements in dye – amplifier (Ti : sapphire) has become by far the most common
chains,.12/ allowed the exciting field of femtochemistry laser material for the generation of ultrashort pulses.
to be developed,.13/ which will be discussed briefly in Developed in the mid-1980s,.21/ Ti : sapphire has a gain
section 5.1, and the generation of 6-fs probe pulses,.14/ a bandwidth from 700 to 1100 nm peaking around 800 nm,
record which stood until very recently. Self mode-locking the broadest of the solid-state materials yet discovered,
in Ti : sapphire-based lasers was discovered.15/ in 1990 high-gain cross-section and extremely good thermal
and the early 1990s brought a new revolution – simplicity conductivity. Mode locking is achieved through the action
of use – and, with it, the commercialization of ultrashort of an instantaneous nonlinear Kerr lens in the laser rod
pulse technology. Ti : sapphire oscillators now produce (see section 3.1). The peak fluence of the laser approaches
10 – 20-fs pulses routinely and 4 – 5-fs pulses in optimized 1011 W cm 2 , which is enough to focus the beam as it
configurations using mirrors designed to reverse the travels through the gain medium on each pass. This Kerr
‘‘chirp’’ introduced by the Ti : sapphire rod. The limiting lens then couples the spatial and temporal modes and
factor on the exceptional stability of these oscillators maintains phase locking.
is the pump source and here diode-pumped solid-state A basic oscillator – cavity configuration.22/ is shown
laser sources are rapidly replacing large, expensive, low- schematically in Figure 1. The laser is pumped by about
efficiency ion lasers. 5 W from a continuous wave (CW) laser source, usually
In parallel with improvements in oscillator technol- now an intracavity-doubled diode-pumped neodymium
ogy, the technique of chirped pulse amplification.16/ laser. This light is focused into the Ti : sapphire rod,
using solid-state gain media in regenerative or multi- collinearly with the laser axis, through the back of one of
pass schemes has replaced the dye – chain amplifiers of the mirrors. The cavity consists of a Brewster-angle cut
the past. A typical amplifier for routine chemistry appli- Ti : sapphire rod, 5 mm or less in length, doped to absorb
cations produces 1 mJ per pulse at a 1-kHz repetition about 90% of the incident pump radiation, two concave
rate or 100 mJ at 10 – 20 Hz with a duration between 20 focusing mirrors placed around it, a high reflector and
and 100 fs. Moreover, a Ti : sapphire laser oscillator and an output coupler. A pair of Brewster-cut fused-silica
amplifier combination can be purchased in a single box prisms are inserted to control the spectral dispersion
less than 1 m square, operating at mains voltages with (chirp) introduced in the laser rod. Dispersion arises
no external water-cooling requirements. Total hands-off from the variation of the refractive index of the material
operation is a reality and, in fact, the complete laser across the gain bandwidth of the laser, which can lead to
system can be computer controlled. a temporal separation of the resonant wavelengths and
In the next section, we shall describe the technology
behind Ti : sapphire lasers and amplifiers and discuss how λ/2
light at almost any frequency from X-rays to terahertz can Pump laser (~5W CW)
be generated and employed by the chemist. A history of
the field can be found in the papers submitted to the bien- P4
M2 P3
nial conference ‘Ultrafast Phenomena’, the proceedings
M1
of which are published in the Springer Series in Chemical
Physics, which is now in its eleventh volume..17/ HR L P2
Ti:sapphire OC
(10%)
P1
2 ULTRAFAST LASERS AND AMPLIFIERS
2.1 Oscillators Figure 1 Diagram of a basic self-mode-locked Ti : sapphire
oscillator showing the cavity layout. The pulse is coupled out
Ultrashort pulses are generated by mode-locked lasers. from the dispersed end of the cavity, which requires a pair of
By constructive interference, a short pulse is formed matching extracavity prisms.
ULTRAFAST LASER TECHNOLOGY AND SPECTROSCOPY 3
A bandwidth-limited pulse has a spectral width given j0 is the group delay, j00 the group delay dispersion
by the Fourier transform of its time-domain profile. (GDD) [or group velocity dispersion (GVD)] and j000
4 GENERAL ARTICLES
n
1.6
2 ln 2t2
Ein .t/ D E0 exp C iw0 t .3/
tin 2 B
1.5
The electric field after traveling through a dispersive A
medium can be found by transforming Ein to the fre-
500 1000 1500 2000 2500 3000
quency domain and adding the components from the
phase expansion j.w/ in Equation (1) before transform- (a) λ (nm)
ing back. If we assume only a contribution from the GDD
term, the electric field Eout is given by Equation (4):.18/ 0.2
C
Eout .t/ D E0 exp i.w0 t j/ .t j0 /2 .4/ D
where (Equation 5) B
0.0
1 A
t2in
D C 2ij00 .5/ −0.1
2 ln 2
The effects of this dispersion are twofold. First, by −0.2
inspection of the Gaussian part of Eout , tout is analogous
to tin from Ein and is broadened with respect to the 500 1000 1500 2000 2500 3000
input-pulse width by a factor (Equation 6) (b) λ (nm)
s
tout j002 Figure 3 (a) Refractive index versus wavelength data for some
D 1 C 4 16.ln 2/2 .6/ common materials: (A) fused silica, (B) Schott BK7, (C) Schott
tin tin SF10 and (D) sapphire. The points are measured values and the
lines are fits to Sellmeier equations. (b) The GDD for 1 mm of
Second, a frequency sweep is introduced in the output material derived from the fits.
pulse (because the expression in Equation (5) is complex)
with a sign that is opposite to that of j00 . 200
The GDD, j00m , due to material of length lm , is related
Output pulse width (fs)
G1 G2
lp
α γ L1 L2
ϕ1
b ϕ2 M
p1 lg lg
r
Figure 6 Schematic diagram of a grating-pair pulse stretcher
(a) p2 showing the arrangement for positive dispersion. G1 and G2 are
diffraction gratings, L1 and L2 are identical lenses separated by
twice their focal length, f , and M is a mirror acting to double-pass
the beam through the system. The distance lg – f determines the
total dispersion.
p1
TOD (fs3)
GVD (fs2)
Figure 5a) is
−100 0
2wlp
j.w/ D cos jbluest
2 j2 .8/ −150 −500
c
where j2 is the (frequency-dependent) exit angle, D jbluest −200
2 −1000
j2 .wbluest / is the exit angle of the shortest-wavelength light −250
transmitted by the prism pair:
−300 −1500
1 600 700 800 900 1000
j2 .w/ D arcsinfn sin[a arcsin.n sin j1 /]g .9/
where n is the (frequency-dependent) refractive index of the Wavelength (nm)
prism material, j1 is the (frequency-independent) angle of
incidence on the first prism and a is the prism top angle. If Figure 7 The residual GVD and TOD arising from the balance
the prism compressor is designed for frequency wdesign : between the dispersion of a 4.75-mm Ti : sapphire laser rod and
the intracavity silica prism pair separated by 60 cm.
1
a D 2 arcsin q .10/
1 C n2design 2.3 Chirped-pulse Amplification
h a i
j1 D arcsin ndesign sin .11/ The amplification of nanojoule-level femtosecond pulses
2 to the millijoule level and above is complicated by the
where ndesign is the refractive index of the prism at the design extremely high peak powers involved. A 1-mJ 20-fs pulse
wavelength. Expressions for the group delay, GVD, TOD and focused to a 100-µm spot size has a peak fluence of
FOD can be obtained by taking derivatives of Equation (8).
5 ð 1012 W cm 2 . The damage threshold of most optical
The group delay in a grating compressor/stretcher (see Figures 5b materials is only a few gigawatts per square centimeter,
and 6) is 1000 times lower. The problem is overcome by stretching
dj P the pulse in time using dispersion to advantage. This is
D .12/
dw c followed by amplification and subsequent recompression
where the optical pathlength is to the original pulse duration. This technique also has the
benefit of eliminating unwanted nonlinear effects in the
1 C cos q
PDL .13/ amplifier materials. A diagram showing the principle of
cos.g q/
chirped-pulse amplification (CPA) is shown in Figure 8.
2pc The pulse stretcher is a variation of the grating pair
q.w/ D g arcsin sin g .14/
wd described above..32/ A unity-magnification telescope is
with g the angle of incidence on the first grating and d the groove placed between two gratings in an antiparallel rather than
frequency. In the case of a grating compressor, L D lg . In the parallel geometry. This reverses the sign of the dispersion
case of a grating stretcher, L D 2.lg f / cos g.
Expressions for the GVD, TOD and FOD can be obtained by
taking derivatives of Equation (12). For a double-pass grating
compressor/stretcher, the analytical expression
" 2 # 3/2
d2 j l3 L l O S A C
D 1 sin g .15/
dw2 pc2 d2 d
pulse incurs significantly less loss in these arrangements, design is the recompression process. The naive approach
accrues much less chirp and only one pass is made through is to add additional separation between the gratings in
the PC. There is also no need for a Faraday isolator. the pulse compressor and this is how the first systems
Additional power-amplification stages may be added to were built. Unfortunately, the stretcher and compressor
increase the pulse energy further. The ring configuration combination is the most dispersive part of the system and
can be modified by arranging for the beams to cross away a mismatch between the two introduces vast third- and
from the focus to achieve a different saturation fluence. fourth-order contributions to the phase expansion. The
In this configuration, 4 W after recompression at 1 kHz easiest way to correct the TOD is to adjust the angle of
has been obtained..38/ At kilohertz repetition rates, the incidence between the stretcher and compressor, which
presence of a thermally induced refractive index change changes the third-order contribution. Figure 11 (line A)
across the spatial profile of the beam must be avoided shows the net group-delay dispersion versus wavelength
in order to achieve diffraction-limited output. This is for the kilohertz regenerative amplifier discussed above.
achieved either by cooling to 120 K where the thermal The GDD curve is essentially flat over only a narrow
properties of sapphire are much improved.39/ or by using wavelength range although the GDD and TOD are zero
the lens to advantage..40/ At lower repetition rates, the simultaneously at the center wavelength. Table 2 shows
medium has time to recover and a thermal lens is usually the bandwidth (fwhm) of Gaussian pulses of different
not established. In this regime, power amplifiers can be durations. Ideally, the GDD curve should be flat over
added to the limit of available pump energy. An additional perhaps twice the bandwidth to avoid phase distortions.
complication requires that short pulses of more than a few Recall that the third-order contribution from prism
millijoules in energy must be recompressed under vacuum pairs has the opposite sign to gratings..41/ This fact can
to avoid nonlinear effects and ionization of the air. be used to null the GDD, TOD and FOD terms and
this is illustrated in Figure 11 (line B). The difference is
2.4 Pulse Recompression dramatic and this system will support much shorter pulses
at the expense of 2.4 m of pathlength between the SF18
Clearly, the amplification process introduces extra dis-
prism pair.
persion and one of the major considerations in system
Another method in the recent literature.42/ uses grat-
ings of different groove density in the compressor
8
compared with the stretcher balanced against additional
round trips in the amplifier. This method, while bet-
ter than the angular adjustment technique, is not as
GVD (103 fs2)
6
effective as the grating – prism combination approach,
A although it has found favor in commercial application
4
owing to its inherent compactness. Typical parameters
are a 1200 lines mm 1 grating in the stretcher at an angle
2 of incidence of only 6° and 2000 lines mm 1 in the com-
B pressor at 57° , which is reasonably close to Littrow
0 geometry (55° ). Gratings with 2000 lines mm 1 are sig-
C nificantly more efficient than those with 1200 lines mm 1 ,
760 780 800 820 840 giving improved throughput in the compressor. However,
a combination of mixed gratings and a prism pair as shown
λ (nm)
in Figure 11 (line C) is a little better than matched grat-
Figure 11 Solid line (A): the net GVD due to the stretcher – ings and prisms with the benefit of extra throughput and
amplifier – compressor combination using 1200 lines mm 1 diff- reduced prism separation without the need to balance the
raction gratings. The difference between the angle of incidence
in the stretcher compared to the compressor is 10.32° and the Table 2 Pulse duration versus bandwidth
extra grating displacement is 69.4 mm. Dashed line (B): the (fwhm) for Gaussian-shaped pulses centered at
same using 1200 lines mm 1 gratings in combination with an 800 nm
SF18-glass prism pair. The difference between the angle of
incidence in the stretcher compared with the compressor is Gaussian pulse Gaussian bandwidth
3.4° and the extra grating displacement is 26.2 mm. The prism duration (fwhm) (fs) (fwhm) (nm)
separation is 2.4 m. Dashed-dotted line (C): the same, using
a 1200 lines mm 1 diffraction grating in the stretcher and an 100 9.4
1800 lines mm 1 grating in the compressor in combination with 50 18.8
an SF10-glass prism pair. The angle of incidence in the stretcher 30 31.3
is 13° and in the compressor 39° . Littrow is 41° . The prism 10 94
separation is 1.65 m.
ULTRAFAST LASER TECHNOLOGY AND SPECTROSCOPY 9
total dispersion with extra amplifier material..43/ This sys- a wavelength. As an example, consider the propagation of
tem will support 20-fs pulses with little phase distortion. femtosecond pulses through an optical fiber. With a 9-µm
fiber-core diameter (typical for communications-grade
fiber), 10-nJ pulse energy and 100-fs pulse width, the
2.5 Saturation Effects
peak power is 100 kW, corresponding to a power density
The gain cross-section, sg , is not constant as a function of 1.5 ð 1011 W cm 2 . If the length of the fiber is 1 cm, the
of wavelength. Since this appears as an exponent in optical pathlength changes by Ln2 I D 472 nm or half a
calculating the total gain, successive passes through wavelength. From this calculation, it can be seen that the
the amplification medium can lead to pulse spectral OKE can have a significant effect on a femtosecond pulse
narrowing and a shift in the central wavelength. This limits traveling through a medium. For pulses with energies
the maximum bandwidth to 47 nm in Ti : sapphire..38/ As in the order of millijoules or higher, even the nonlinear
the gain approaches saturation, the leading red edge of the refractive index of air becomes important.
pulse extracts energy preferentially and the spectrum will To understand how the OKE can modify the spectral
red shift. The maximum gain bandwidth can be achieved properties of an ultrashort pulse, one has to consider how
by seeding to the blue of the peak, allowing the gain to the nonlinear refractive index modifies the optical phase
shift towards the maximum on successive passes. Second, of the pulse. The electric field of a laser pulse traveling in
by altering the gain profile by discriminating against the the x direction can be written as Equation (19):
peak wavelengths using an étalon or a birefringent filter,
termed regenerative pulse shaping, the theoretical limit E.t/ cos.wt kx/ .19/
can be overcome..44/
where k D wn/c is the wavenumber. Since the wavenum-
ber depends on the (nonlinear) refractive index of the
medium, the pulse will acquire a time-dependent phase
3 WAVELENGTH CONVERSION induced by the Kerr effect. Inserting Equation (18)
into Equation (19) and performing a Taylor expansion
Ultrafast lasers and amplifiers typically operate at a very around the peak of the ultrashort pulse, one finds
limited range of wavelengths. For example, Ti : sapphire- (Equation 20)
based ultrafast lasers are tunable in the near-infrared
(NIR) region from about 700 to 1000 nm but typically E.t/ cos[.w C xt/t kx] .20/
work best at about 800 nm. The high peak power of these
where x depends on the nonlinear refractive index, the
lasers can be used, however, to convert the laser light to
pulse width and peak power, and the distance traveled.
different wavelengths. In fact, in some cases ultrafast laser
Consequently, the nonlinear refractive index induces
systems may be the ideal or only route to make radiation
an approximately linear frequency sweep (or chirp, see
at certain wavelengths. Below, a series of techniques are
section 2.2 and Figure 12) on the pulse. In other words,
described to convert femtosecond laser pulses at visible
the spectrum of the pulse has broadened owing to the
wavelengths to other wavelengths.
nonlinear interaction. If a single pulse modifies its own
characteristics in this way, the effect is often referred
3.1 White-light Generation and the Optical Kerr Effect to as self-phase modulation. If one pulse modifies the
At high intensities such as on the peak of an ultrashort effective refractive index causing a second pulse to
laser pulse, the refractive index of any medium becomes change its characteristics, this is referred to as cross-phase
a function of the incident intensity. This effect, which is modulation.
often referred to as the optical Kerr effect (OKE),.45/ can The spectral broadening induced by the nonlinear
be described by Equation (18): refractive index is extremely useful in spectroscopic
applications. For example, an 800-nm femtosecond pulse
n.I/ D n0 C n2 I C Ð Ð Ð .18/ can be sent through a short length of fiber or through a few
millimeters of glass or sapphire to produce a broadband
where n0 is the normal refractive index of the medium output pulse. Often there will be significant power at
and n2 is the nonlinear refractive index. The nonlinear wavelengths ranging from 400 nm to 1.6 µm. For this
refractive index is very small, for example, in fused reason, such spectrally broadened pulses are referred to as
silica n2 ³ 3 ð 10 16 cm2 W 1 . A laser pulse with center white-light continuum pulses. The white-light continuum
frequency w traveling through a medium of length L generated in a fiber has been used to generate some of the
will acquire an optical phase wLn/c and therefore the world’s shortest pulses of around 5 fs..46,47/ A white-light
effects of the nonlinear refractive index will become continuum pulse is an ideal seed for an optical parametric
important when this phase factor becomes comparable to amplifier (see section 3.3).
10 GENERAL ARTICLES
ω(t )
I(t )
−0
eration (SHG), third-harmonic generation (THG) and
fourth-harmonic generation (FHG) to produce fem-
tosecond pulses in the near- to deep-ultraviolet (UV)
region. However, the group velocity of the pulses
(see section 2.2) depends on the center wavelength and
0 changes significantly as the UV region is approached. For
−2 0 2
example, in a 1-mm b-barium borate (BBO) crystal (suit-
(a) Time
able for harmonic generation down to about 180 nm) the
difference in group delay between the fundamental and
the fourth harmonic is 3.3 ps (see Table 3). Depending
on the set-up, this implies that the conversion efficiency
is very low or the pulses produced are very long..48/
Therefore, when UV pulses are produced, it is extremely
important to use the thinnest possible nonlinear crystals.
As a rough guide, one should choose the thickness of
the crystal such that the group-delay difference between
the fundamental and the harmonic is about equal to or
less than the width of the pulse. An efficient harmonic-
generation set-up will also use multiple conversion steps
(b) and between steps readjust the relative time delay
between the laser pulses at different wavelengths..49/
Figure 12 (a) Chirp on an ultrashort pulse induced by the non- Most nonlinear crystals used for harmonic generation
linear refractive index of a dielectric medium. The input pulse
has a sech2 envelope and the figure shows the instantaneous fre- [BBO, lithium triborate (LBO), potassium dihydrogen-
quency within the pulse. A Taylor expansion around the peak of phosphate (KDP), etc.] are opaque in the deep-UV
the pulse shows that the frequency sweep is approximately linear region. Very high harmonic generation in low-pressure
around time zero. (b) Photograph of a femtosecond white-light gases has been used successfully to generate deep-UV and
continuum beam generated in a piece of sapphire. (Picture cour- soft X-ray pulses. It was recently shown.50/ that a glass
tesy of the Center for Ultrafast Optical Science, University of
Michigan.) capillary could be used to modify the phasematching
condition for coherent soft X-ray generation. Using this
set-up, femtosecond pulses at 800 nm were converted to
An implication of the nonlinear refractive index is the 17 – 32-nm wavelength range (¾30th harmonic) with
self-focusing or defocusing. As a laser beam is typically about 0.2 nJ energy per harmonic order. A similar set-up
more intense in its center, the nonlinear change of the was used.51/ to mix 800- and 400-nm pulses to produce 8-fs
refractive index will be strongest in the center. As a result, pulses at 270 nm. Extremely short (5 fs) amplified laser
the medium will act as an intensity-dependent lens. In a pulses have been used.52/ to generate X-rays (¾4 nm) in
set-up in which the sample is translated through the focus the water window by harmonic generation in a gas jet.
of a beam, this effect can be used to measure the nonlinear
refractive index of a sample quickly. Self-focusing is the
Table 3 Group delays calculated
basis of the Kerr lens mode locking (KLM) effect used from the refractive index of BBO,
in ultrashort lasers (see section 2.1). Self-focusing can of femtosecond pulses at various
become a run-away process leading to beam distortion wavelengths traveling through a
and catastrophic damage to optical components. In 1-mm crystal (ordinary polarization)
white-light generation, self-focusing can result in the
Wavelength tgroup tgroup
beam breaking up into multiple filaments that make the (nm) (ps) (ps)
white-light output extremely unstable. It is therefore of
the utmost importance to choose the incident power such 800 5.62 –
that white light is generated without producing multiple 400 5.94 0.32
267 6.74 1.12
filaments. For a 100-fs pulse, this usually means that the 200 8.97 3.34
pulse energy should be limited to approximately 1 µJ.
ULTRAFAST LASER TECHNOLOGY AND SPECTROSCOPY 11
The advantage of very high harmonic generation is that produce enormous parametric gain without destroying
the X-rays are generated in a well-collimated beam. The the nonlinear crystal.
disadvantage is that it has not yet been shown to be pos- The frequencies or wavelengths that are produced in
sible to generate hard X-rays with wavelengths smaller OPG or OPA depend on the phasematching condition,
than a molecular bond length. group velocity walk-off and the type of crystal used.
Electron impact sources could generate femtosecond Figure 13(b) shows materials that are commonly used for
hard X-rays if high-charge, high-energy femtosecond parametric generation in the IR region. BBO has a limited
electron bunches were available. Even so, electron tuning range in the IR range (approximately 1.2 – 2.8 µm
impact sources have the disadvantage that the X-rays when pumped at 800 nm) but is very efficient owing to the
are emitted in a 2p solid angle, which makes their small group-velocity walk-off and high damage threshold.
brightness typically very low. Therefore, these sources KTP and its analogs rubidium titanyl phosphate and
are difficult to use in diffraction experiments although cesium titanyl phosphate (RTA and CTA) are not as
not strictly impossible. Very high-power laser pulses efficient as BBO but allow the generation of femtosecond
[peak powers of the order of 1 TW (1012 W)] can be pulses at wavelengths as long as 3 – 4 µm. There is a
used to generate laser-produced plasmas..53/ Typically, variety of crystals suitable for generation of pulses in
a high-power laser pulse is used to evaporate a (metal) the mid-IR region such as AgGaS2 and GaSe. However,
target and produce a plasma by stripping electrons off the when these crystals are used to convert directly from
atoms with multiphoton ionization..54/ Recombination of the visible to the mid-IR, they suffer from enormous
these electrons with the ions results in the emission of group velocity walk-off, (two-photon) absorption of the
hard X-ray pulses (wavelengths of the order of 1 Å). pump and very poor efficiency. Therefore, generating
Very recently, it has been shown that reverse Thompson mid-IR pulses is typically performed in a two-stage
scattering of terawatt laser pulses off a high-energy
(50 MeV) electron beam can be used to produce hard
X-rays (0.4 Å)..55/ However, only 104 X-ray photons
were generated per laser shot, resulting in about one
diffracted X-ray photon per shot in diffraction off
Si h111i.
ω1
ω1 + ω2
3.3 Optical Parametric Amplifier for Infrared
Generation
The infrared (IR) region of the spectrum is very important ω2
for the sensing of a great variety of (transient) molecular
species. Femtosecond IR pulses can be used to determine (a)
which bonds in a molecule break or form. The mid-
GaSe
IR fingerprint region is ideally suited to determine the
presence of specific molecules in a sample. Therefore, AgGaS2
a great deal of effort has been invested over the last Terahertz methods KTP
decade to produce femtosecond pulses tunable in the
BBO
near- and mid-IR regions. Most techniques in use now
Frequency (cm−1)
are based on parametric difference-frequency processes
(see Figure 13a and b)..56/ In difference-frequency mixing, 10 100 1000 10 000
a strong femtosecond pulse at frequency w1 C w2 mixes Translations Fundamental
in a nonlinear crystal with a (weaker) pulse at frequency vibrations
Librations Overtone
w1 , to produce a new beam of femtosecond pulses at (b) vibrations
frequency w2 . If the incident power at frequencies w1
Figure 13 (a) Difference-frequency mixing. A strong fem-
and w2 is zero, a nonlinear crystal can produce these tosecond pulse at frequency w1 C w2 can mix in a nonlinear
frequencies spontaneously in a process referred to as crystal with a (weaker) pulse at frequency w1 , to produce a
optical parametric generation (OPG). If the incident new beam of femtosecond pulses at frequency w2 . (b) Diagram
power at frequencies w1 and w2 is small but nonzero, showing the various femtosecond IR tuning ranges that can
the pump pulse at frequency w1 C w2 can amplify the be obtained using an optical parametric amplification (OPA).
Using the common crystals BBO and potassium titanyl phos-
former frequencies in what is referred to as OPA. Since phate (KTP), tuning between 1 and 3 µm can be obtained. With
the peak power of a femtosecond pulse can be extremely the more unusual crystals AgGaS2 , AgGaSe2 and GaSe, one
high while the pulse energy is relatively low, one can can obtain radiation to wavelengths as long as 20 µm.
12 GENERAL ARTICLES
t
S
pu
inp
ut
tocurrent. Since the visible beam has to be focused to
zo
ut
the probe pulse, one can record a time-domain trace as a seed for electron accelerators or for the genera-
of the electric field of the terahertz pulse. Using this tion of femtosecond X-ray pulses. Current technology for
method, signal-to-noise ratios, defined as the ratio of the generating femtosecond electron pulses is based on exper-
terahertz pulse peak to the noise background, as high iments done in the past with picosecond and nanosecond
as 107 have been reported..68/ However, the signal-to- laser pulses..71 – 73/ A UV laser beam is used to irradiate a
noise ratio with which one can measure the peak of metal target. If the photon energy is higher than the work
the terahertz pulse is typically of the order of 102 – 103 function of the metal (typically 4 – 5 eV for common tran-
in 100 ms. An exciting new variation on this technique sition metals such as gold, silver or tungsten), electrons
is the use of a chirped probe pulse..69/ A femtosecond are ejected into the vacuum through the photoelec-
pulse at 800 nm can be stretched and chirped to tens of tric effect. These emitted electrons are electrostatically
picoseconds using a grating pair. If this chirped pulse is extracted and accelerated into a narrow beam. In recent
used in the electrooptic sampling process, there will be a experiments (see section 5.3), this technique has been
relationship between wavelength and relative time delay. brought into the subpicosecond domain. The main prob-
Thus, detection of this probe pulse with a spectrometer lem in maintaining the time resolution is the space-charge
and diode-array detector allows one to measure the entire effect: nonrelativistic electrons repel each other through
terahertz pulse shape in a single laser shot. Coulomb repulsion. It is therefore of the greatest impor-
As rectification and electrooptic sampling are nonres- tance to accelerate the electrons as quickly as possible
onant effects, the minimum duration of the terahertz and to keep the number of electrons per pulse as low as
pulses that can be generated or detected is limited only possible. Thus, it was seen in an experiment.74/ that for a
by the thickness of the crystal scaled with the difference 100-µm laser spot size on the photocathode, the electron
in phase and group velocity. Thus, with ca. 10 – 15-fs excit- pulse would broaden to about 15 ps when there were
ing pulses at 800 nm, it was shown that terahertz pulses 1000 electrons in the pulse. When the number of elec-
could be generated with detectable frequencies as high trons per pulse was reduced to 100, the pulse width was
as 70 THz..70/ At these large bandwidths, it is unavoid- less than 1 ps. There is no fundamental reason why one
able that the t-ray spectrum will overlap with a photon could not work with ten or even one electron per pulse
absorption band in the generating and detecting crystals, and therefore it should be possible to achieve electron-
leading to large oscillations in the terahertz field trailing pulse durations in the order of tens of femtoseconds. Of
the main peak. course, to achieve a reasonable signal-to-noise ratio in an
The current record highest detectable frequency for experiment, the pulse repetition rate should be high. Such
a terahertz pulse is ¾70 THz, but there is no reason to pulses will be of great value in time-dependent molecular
believe that this could not be improved upon. Using structure determination.
the simple time – bandwidth relation, nt D 0.32, it
follows that with the shortest visible pulses achievable,
ca. 4 – 5 fs, usable power at frequencies from 0 to 160 THz 4 TIME-RESOLVED EXPERIMENTS
(l D 1.8 µm) could be achieved. As femtosecond lasers
continue to shrink in size, it may be expected that Most electronic devices cannot measure transients much
ultrafast terahertz devices may well take over from faster than about 1 ns. Although there are specialized
Fourier transform infrared (FTIR) spectrometers as electronic devices such as streak cameras that may be able
general-purpose IR spectrometers. As an entire terahertz to resolve picosecond or even hundreds of femtosecond
time-domain trace can be acquired in a single shot,.69/ transients in real time, in most cases it makes more
these devices would combine the reliability and accuracy sense to look for alternative detection techniques. The
of FTIR spectrometry with real-time speeds. The most techniques that are used most frequently are based on
significant aspect of ultrafast terahertz pulses, however, auto- or cross-correlation of two beams of femtosecond
is that they are synchronized with visible or UV pulses, pulses (see Figure 16a). If the sample is a nonlinear crystal
allowing time-domain spectroscopy. used for sum-frequency generation, this technique can be
used to determine the shape and relative arrival time
3.6 Femtosecond Electron Pulses of two short pulses. If the sample contains molecules or
atoms that resonantly absorb the incident radiation, the
Very short (picosecond to femtosecond) electron pulses experiment is a pump – probe experiment.
are useful for a variety of applications. For example,
picosecond electron pulses have been used as a
4.1 Auto- and Cross-correlation
probe pulse for determining the time-dependent struc-
ture of molecules undergoing chemical reactions (see In an autocorrelator, an incoming beam of pulses is split
section 5.3). However, such pulses might also be used in two. One beam travels through an optical path with
ULTRAFAST LASER TECHNOLOGY AND SPECTROSCOPY 15
Table 4 Second-order autocorrelation functions and time – bandwidth products for various pulse-shape models,.76/ where
tp D pulse width (fwhm), tG D autocorrelation width (fwhm) and n D spectral width (fwhm)
(AB)**
(AB)*
Fluorescence
fs-probe
A+ + B−
fs-pump
A+B
AB
(a)
(a) 6
0
N A
−20 + 4
H2N S NH2
∆OD (mOD)
B
Signal
−40
−60 2
−80 C
0
0.0 0.2 0.4 0.6 0.8 −2 0 2 4 6 8
Figure 20 (a) Schematic diagram of a vibronic transition Figure 21 (a) Simple diagram depicting a typical coherent
excited by a pulse whose width is smaller than the vibrational dissociation reaction. The pump pulse excites a small molecule
period. The pulse creates a coherent vibrational wavepacket in to its first excited state. If the pump pulse is shorter than
the excited electronic state that will oscillate in the excited-state the vibrational period, it may create a coherent wavepacket
potential well. (b) Time-resolved 600-nm pump, 700-nm probe that will oscillate in the excited-state potential well. In this
signals in the dye molecule thionine studied with 42-fs time diagram, the molecule splits into two fragments consisting of
resolution. The signal is stimulated emission from the excited either two radicals or two ions. A probe pulse excites the
electronic state and the oscillations correspond to a vibrational molecule to a third state, from which it fluoresces back to the
mode at 443 cm 1 in the excited-state potential well. ground state. The total fluorescence is measured as a function
of pump – probe delay. (b) Pump – probe results.86/ from NaI
with lpump D 310 nm. (A) lprobe D 580 nm; (b) lprobe D 589 nm
in the bound state. However, if the sodium radical is (on resonance); and (C) lprobe D 612 nm. (Reproduced from
probed by inducing fluorescence with the probe pulse, it Rosker et al..86/ by permission of Elsevier Science. Elsevier
Science BV, 1988.)
is seen that the population of the radical increases in a
stepwise fashion. Therefore, such an experiment shows
that the chemical reaction (a dissociation in this case) phase with that in the condensed phase..87/ Various
is a quantum-mechanical process in which a fraction of molecules that had been studied in the gas phase have
the bound wavepacket tunnels to the state of dissoci- now been studied in solution where again one could
ated radicals each time the wavepacket travels through observe quantum beats due to vibrational wavepackets.
the crossing region. Interestingly, it is possible to use Examples are HgI2 .88/ and I2 ..89,90/ Vibrational quantum
quantum mechanical interference of wavepackets to steer beats have now been observed in a large variety of
a reaction in a desired direction and away from undesired molecules in the condensed phase, including proteins..91/
directions. This is referred to as coherent control and has In these large, complicated systems, quantum beats
been applied on small molecules with varied success..85/ provide a unique opportunity to determine the potentials
A study, such as that on NaI described above, becomes relevant for chemical and biological reactions. Not least,
interesting if one can compare the behavior in the gas the femtochemistry technique may be used to detect
20 GENERAL ARTICLES
5.2 Imaging
Nonlinear ultrafast optics can be of immense value for (a)
(biological) imaging studies. Femtosecond lasers can
be used to perform multiphoton absorption confocal-
imaging studies. Using this technique, one can image the
spatial distribution of one specific molecule inside a living 150
cell..92/ Tunable femtosecond NIR pulses are ideal for
this purpose as scattering and damage to the cell are 200 21
Delay (fs)
17
12
m)
x(
the beam. Owing to the long wavelengths at ca. 1 THz, electron-diffraction experiments have so far only been
spatial resolution was limited to about 1 mm. However, performed in the gas phase and on surfaces. However,
because the transit time of subpicosecond terahertz pulses as steady-state electron diffraction has also been used to
can be measured with an accuracy of a few femtoseconds determine the structure of proteins in the solid state,.105/
(see Figure 22b), it is possible to make tomographic femtosecond time-resolved electron diffraction in the
images..100/ Thus, by measuring the internal reflections solid state may also become a possibility. Electrons
in a sample, for example, the various surfaces in a at present provide the most structural information
floppy disk, it is possible to detect hidden features with a for a given amount of radiation damage..106/ The
depth resolution much higher than the wavelength. Very atomic cross-section of carbon for (elastic or inelastic)
recently, several attempts have been made to improve scattering of electrons is more than six orders of
the lateral resolution by applying near-field techniques magnitude larger than that of X-rays. Furthermore,
such as using small apertures in front of the sample.102/ or radiation damage by 80 – 500-keV (l D 0.043 – 0.017 Å)
terahertz pulse generation in subwavelength regions..99/ electrons is 400 – 1000 times less than that of l D 1.5 Å
It was shown recently.103/ that electrooptic sampling can X-rays..106/ Clearly, it would be a great advantage if
be performed in parallel using a large-area electrooptic one could apply the technique of diffraction on a
crystal and an unfocused probe beam, thus allowing the femtosecond timescale. Modern synchrotron facilities
acquisition of t-ray images in real time. such as the European Synchrotron Radiation Facility
Using a technique analogous to ultrasound, optical- (ESRF) in Grenoble, France, and the Advanced Light
coherence tomography utilizing femtosecond lasers has Source (ALS) in Berkeley, CA, USA, now make it
permitted micrometer resolution in real-time imag- possible to study structural dynamics using time-resolved
ing applications, particularly in biomedicine..104/ Cross- X-ray crystallography on a nanosecond timescale..107,108/
sectional images are made in a similar manner to the However, many chemical and biological reactions take
terahertz-imaging application by measuring the ‘‘echo’’ place on a picosecond or even femtosecond timescale.
time of backscattered light using interferometric meth- Many research groups around the world are now
ods. Since the axial resolution is limited by the coherence working towards the goal of femtosecond timescale
length of the light, short-pulse Ti : sapphire and partic- diffraction. The technology of generating femtosecond
ularly NIR Cr : forsterite lasers are seen as attractive X-ray or electron pulses is described in sections 3.2
sources. An image is measured by building up the and 3.6.
backscattered pattern at several transverse positions and A series of (sub)picosecond time-resolved electron-
these high average-power lasers are ideal for imaging at diffraction experiments was recently performed on
a few frames per second. gas phase samples in a molecular beam (Figure 23a
and b)..109,110/ In these experiments, electron pulses were
generated by exciting a back-illuminated photocathode
5.3 Structure Determination: Electron Beams and
with 400-fs 307-nm laser pulses at a 30-Hz repetition
X-rays
rate. The electron pulses (¾6000 electrons) were then
Time-resolved pump– probe spectroscopy has been used accelerated to 18.8 keV and focused with the 307-nm
for a long time to study chemical reactions. Often such pump beam into a gas jet containing the sample. Two-
spectroscopy relies on excitation and probing at visible dimensional electron diffraction patterns were recorded
wavelengths and transient visible spectra have to be as a function of pump – probe delay using a CCD camera
carefully analyzed and interpreted to find out what the fiber-coupled to an image intensifier. The time resolu-
reaction products are. More recently, several groups have tion (determined by space – charge effects) was about
started to use femtosecond IR pulses in the hope that 7 ps. In these experiments, dissociation reactions in, for
transient IR spectra will give more direct information example, CF2 I2 and Fe(CO)5 were studied. The method
about which chemical bonds are broken or formed. allowed the observation of rare reaction intermediates
However, neither visible nor IR spectroscopy provides and, most importantly, the determination of their spatial
direct information about the spatial atomic structure of a structure. Picosecond time-resolved electron diffraction
given reaction intermediate. experiments have also been performed on surfaces. For
X-ray diffraction has been used for close on a example, the effect of melting a Pb (110) surface has been
century to determine the atomic structure of crystals. studied..72/
Especially in the life sciences this has resulted in a much Generating femtosecond hard X-ray pulses is much
better understanding of the structure of proteins and more difficult than generating electron pulses, which may
other biomolecules and hence to a better understanding explain the small number of unique experiments..53/ All
of the fundamentals of biochemistry. Because of the ultrafast X-ray diffraction experiments to date.53,111/ have
great absorption of electrons by materials, time-resolved studied the lattice expansion of semiconductors, metals
22 GENERAL ARTICLES
Environment: Trace Gas Monitoring (Volume 3) the Photoinduced Intramolecular Electron Transfer of
Environmental Trace Species Monitoring: Introduction Capped Porphyrins’, Chem. Phys., 104(2), 315 – 324
ž Laser Absorption Spectroscopy, Air Monitoring by (1986).
Tunable Mid-infrared Diode ž Laser-induced Breakdown 6. J.R. Miller, J.V. Beitz, R.K. Huddleston, ‘Effect of
Spectroscopy, Elemental Analysis Free Energy on Rates of Electron Transfer Between
Molecules’, J. Am. Chem. Soc., 106(18), 5057 – 5068
Environment: Water and Waste (Volume 3) (1984).
Infrared Spectroscopy in Environmental Analysis 7. R.A. Marcus, ‘ET’, J. Chem. Phys., 24, 966 – 978 (1956).
8. R.M. Bowman, K.B. Eisenthal, D.P. Millar, ‘Frictional
Peptides and Proteins (Volume 7) Effects on Barrier Crossing in Solution – Comparison
with the Kramers Equation’, J. Chem. Phys., 89(2),
X-ray Crystallography of Biological Macromolecules
762 – 769 (1988).
9. M.G. Hyde, G.S. Beddard, ‘Picosecond Photodisso-
Atomic Spectroscopy (Volume 11)
ciation and Geminate Radical Recombination in
Laser Ablation in Atomic Spectroscopy ž Laser-induced
Alkane Solutions of Tetraphenylhydrazine’, Chem.
Breakdown Spectroscopy Phys., 151(2), 239 – 248 (1991).
10. R.L. Fork, B.I. Greene, C.V. Shank, ‘First CPM’, Appl.
Electroanalytical Methods (Volume 11) Phys. Lett., 38(9), 671 – 672 (1981).
Ultrafast Electrochemical Techniques 11. J.A. Valdmanis, R.L. Fork, ‘prism CPM’, IEEE J. Quan-
tum Electron., 22, 112 – 118 (1986).
Electronic Absorption and Luminescence (Volume 12) 12. R.L. Fork, C.V. Shank, R.T. Yen, ‘10 Hz Amp’, Appl.
Fluorescence Imaging Microscopy ž Fluorescence Life- Phys. Lett., 41(3), 223 – 225 (1982).
time Measurements, Applications of 13. A. Zewail, The Chemical Bond. Structure and Dynamics,
Academic Press, Boston, 1992.
Infrared Spectroscopy (Volume 12) 14. R.L. Fork, C. Brito, C.H.P.C. Becker, C.V. Shank,
Infrared Spectroscopy: Introduction ‘Compression of Optical Pulses to Six Femtoseconds
by Using Cubic Phase Compensation’, Opt. Lett., 12,
Kinetic Determinations (Volume 12) 483 – 485 (1987).
Kinetic Determinations: Introduction 15. D.E. Spence, P.N. Kean, W. Sibbett, ‘60-fs Pulse Gen-
eration From a Self-mode-locked Ti – Sapphire Laser’,
Kinetic Determinations cont’d (Volume 13) Opt. Lett., 16(1), 42 – 44 (1991).
Instrumentation for Kinetics 16. D. Strickland, G. Mourou, ‘Compression of Amplified
Chirped Optical Pulses’, Opt. Commun., 55(6), 447 – 449
Mass Spectrometry (Volume 13) (1985).
Time-of-flight Mass Spectrometry 17. T. Elsaesser, J.G. Fujimoto, D.A. Wiersma, W. Zinth
(eds.), Ultrafast Phenomena XI (formerly Picosecond
X-ray Spectrometry (Volume 15) Phenomena), Springer, Berlin, Vol. 63, 1998.
Structure Determination, X-ray Diffraction for ž Ultra- 18. A.E. Siegman, Lasers, University Science Books, Mill
Valley, CA, 1986.
fast Diffraction Techniques
19. O. Svelto, Principles of Lasers, 3rd edition, Plenum Press,
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